Azo guanamines



i atented jan. 3,

AZO GUANAIVHNES Iack Theo Thurston and Donald William Kaiser,

Riverside, Cnn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application May 20, 1947, Serial No. 749,358

3 Claims. (Cl. 260-153) This invention relates to guanamines having one or more azo groups. The present application constitutes a continuation-in-part of our copending application, Serial No. 556,471, filed September 29, 1944, which in turn is a division of our copending application, Serial No. 409,148, filed August 30, 1941, now Pat. No. 2,425,286.

A number of guanamines have been prepared with various substituents. Some of these guanamines have achieved practical importance as intermediates for the preparation of synthetic resins by condensation with formaldehyde or similar aldehydes. Such resins are colorless or substantially so, and where a colored resinous material is desired, it is necessary to incorporate pigments of various kinds. There is a considerable demand for synthetic resins having colored molecules so that the resin itself is colored for use in coating compositions, plastics, pigments and the like.

When guanamines are prepared with a substituent on one of the amino groups attached to the 4- or G-carbon atom of the ring, it is possible to form azo dyes either by diazotizing the aminosubstituted guanamines and coupling with a suitable coupling component such as phenols, hydroxy carboxylic acid, and thelike, or by producing substituted guanamines having substituents with groups capable of conversion into radicals suitable for azoic coupling with diazotized amines. These azo guanamines are coloring matters of various shades and can be formed into resins which are themselves colored.

Coloring matters of the present invention include the guanamine radical, that is to say, a 4,6- diamino triazine, with a substituent containing an azo group. This substituent will in general be an arylazoaromatic group in which the aromatic portion of the group may be either carbocyclic or heterocyclic. In the case of an arylazoheterocyclic compound the bond connecting to the guanamine can either be from the aryl or from the heterocyclic portion of the group. The substitution may be either on the 2-carbon atom of the triazine ring or-on one of the amino groups. The compounds described and claimed in this application are characterized by the substituent being on one of the amino groups.

In general, the guanamine compounds to be diazotized and coupled in accordance with the present invention are obtained by reacting a suitable biguanide, such as p-nitrophenyl biguanide. with a suitable alkyl ester in a solvent. The resultant arylnitro aromatic substituted guanamine is reduced to a corresponding arylamino aromatic and/or arylene amino aromatic substituted guanamine which serves as the starting material for the colored compositions of the present invention. a

The present invention broadly is not limited to any particular methods of forming the azo coloring matters, the ordinary methods of diazotization and coupling being applicable, insofar as the solubility of the compound permits. Some of the guanamines are not sufliciently soluble in water or aqueous alkali and require reaction in a, suitable organic medium. This is an advantage of the present invention as the color chemist does not have to learn any basically new techniques.

The azo coloringmatters of the present invention may have one or more guanamine radicals and one or more azo groups. In the case of polyazo compounds the usual methods of producing such polyazo compounds can be followed. Thus, for example, a 'polyamine may be polyazotized and coupled with a plurality of substituted guanamines or an azo guanamine can be prepared having diazotizable amino groups either by diazotizing an amino guanamine and coupling with an amino compound or by diazotizing a polyamine with a blocked amino group, coupling with a guanamine and then freeing the amino group followed by diazotization and renewed coupling, or coupling with another diazo compound. These procedures which are standard in the practical chemistry of azo'dyes are applicable in producing the azo guanamides ofthe present invention, and again it is an advantage that no new techniques are required.

The invention will be described in greater de-:

tail in conjunction with'the following specific examples which are typical illustrations. The parts are by weight.

EXAMPLE 1 P-m'trophenylbiguanide was cooled in an ice bath, the yellow solid filtered, washed with a littlevwater and dried in an oven. A yield of 151 parts of p-nitrophenylbiguanide hydrochloride was obtained which melted with sublimation at 258 C. The free base, prepared by the addition of hydroxide, solution to an aqueous suspension of the hydrochloride melted at, 133 C. with decomposition.

EXAMPLE 2 4-N-p-nitrophenyl formoguanamine To a solution of 22.3 parts of p-nitrophenyl biguanide in a mixtureof 100 parts of methanol 1 zz-cmaeqe wt fer a I sha l a .ev n nsicnw i 5. Rattan; sl ni-ni rop nyl tweets ad in 29D, of methanol was hea ed to boi in undera,-te i z .'c deus.er- A solution to: 54 pants or hl ridein 6. 12 0f spnet i ate hydiz s lex a acid sth m sxaduallx add d m m the. top Qt the n ndensen. Th9 was, removed ibel exoth rmic. TB: etiienlsa tfillemixtl xe. 1m; the a tion. aizqsie sed, the lid dis ent. finally giving rials: yellow additions not selut on was. di ii 1 th can 11 Lum co centrat d-ha I; 121921 me ed. a dinanieeb tht ot a. 1.192 time nearlii cq es minute, lats i tnatatedf rqml c d ieni T e-' r-N-n-ami rum uenaminahxdm nl ide; es fil washed with cold concentrated; hydrochlo-... istacisi. to emove tinsalts then-Wi h ace 9 i and ai m n s; amine; imparts of, mod

EXAMPLE 4' 4-N-phenyl-4' -azo- 4 ""-hydromy-diphenyl) fprmpnunnemma v dicitltiic a dammed ended lka n 7 atom of he; tria ine rina and;

lution containing 2.85 parts of 4-hydroxydiphenyl slowly added, the reaction mixture being kept cold. After the reaction was complete, the free dye was precipitated by acidification with acetic acid and recovered by filtering and washing with water and dried, A v,5'3'a5% yield: of"; tan solid melting at 143 0: was obtained.

r EXAMPLE 5 gAVJL-azophenyl-S 6 -hydromybenzoic acidojormoguanamine COOH i OH Procedure of Example 4 was followed using 5 parts of the guanamine and 2.9 parts of salicyclic acid. A dark brown powder was obtained melting at about 304 C., the yieldbeing 40.6%.

We claim: 1'. An; a zo guanaini ne of the formula N/ N rim-('5' L HR; .N l

inwhichiR is an ary leneazoaromatic radical and he Qn b tween, the nitro en on the a-carhon R is; at nitrogen to carbQniinkage-i 12 -ph nt' -4'- zo-3 '.t4- h im iriphfl' y )-ii rm9ai enamine having; he .tqrmulaz 3;, 4 s nai-azophenyifa cfiv-n dmxybemoie c d) iormoeuanamine having the formula.

Jeers HEO: THURSZTON.

REEERENGES CITED 11 2?: following neferenfifli are of record t e file; of. this Pat nt; 7 UNITED STATES PATENTS;

% a l, Certificate of Correction Patent 2,493,703 January 8, 1950 JACK THEO THURSTON ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 32, for guanamides" read guanamines column 4, line 10, for acidqread acid)- column 4, line 35, for -a.zo-3". read -azo-8- THOMAS F. MURPHY,

Assistant Oommifloner of PM 

1. AN AZO GUANAMINE OF THE FORMULA 